EP0387982A2 - Spray silylation of photoresist images - Google Patents

Spray silylation of photoresist images Download PDF

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Publication number
EP0387982A2
EP0387982A2 EP90300578A EP90300578A EP0387982A2 EP 0387982 A2 EP0387982 A2 EP 0387982A2 EP 90300578 A EP90300578 A EP 90300578A EP 90300578 A EP90300578 A EP 90300578A EP 0387982 A2 EP0387982 A2 EP 0387982A2
Authority
EP
European Patent Office
Prior art keywords
poly
photoresist
dimethylsilazane
image
silylation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP90300578A
Other languages
German (de)
French (fr)
Other versions
EP0387982A3 (en
Inventor
Hiroyuki Hiraoka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
International Business Machines Corp
Original Assignee
International Business Machines Corp
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Filing date
Publication date
Application filed by International Business Machines Corp filed Critical International Business Machines Corp
Publication of EP0387982A2 publication Critical patent/EP0387982A2/en
Publication of EP0387982A3 publication Critical patent/EP0387982A3/en
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G03F7/405—Treatment with inorganic or organometallic reagents after imagewise removal

Definitions

  • Photoresist images have been treated in the past to make them resistant to reactive ion etching.
  • US Patent 4,552,833 shows a vapor phase reaction with hexamethyldisilazane following exposure to radiation.
  • European Patent Application No. 86103208.4 shows the use of a monomeric silylaton agent dissolved in xylene or in the vapor phase. Such processes, however, require the use of a vacuum oven or a reaction bath, and often lead to swelling or cracking.
  • Poly(dimethylsilazane) may be used in a hydrocarbon solvent for silylation of resist images.
  • the advantages of polymeric silylating agents are not only a simplified process, but also no swelling of resist images, because they silylate only surfaces of resist images.
  • the silylation with monomeric agents often results in swelling of resist images, making it unsuitable for high resolution lithography.
  • the oligomeric liquid poly(dimethylsilazanes) were spray coated and placed on a hot plate at 95°C for 30 minutes. After this heating, the wafers were rinsed with xylene for a short period, several seconds, and dried by a nitrogen stream.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

Photoresist images are made resistant to reactive ion etching by treating them with a poly(dimethylsilazane).

Description

  • Photoresist images have been treated in the past to make them resistant to reactive ion etching. US Patent 4,552,833 shows a vapor phase reaction with hexamethyldisilazane following exposure to radiation. European Patent Application No. 86103208.4 shows the use of a monomeric silylaton agent dissolved in xylene or in the vapor phase. Such processes, however, require the use of a vacuum oven or a reaction bath, and often lead to swelling or cracking.
  • US Patent 4,587,205, (at Col. 10 tine 30), shows the spray coating onto a substrate of a polysilane positive photoresist material.
  • US Patent 4,678,688 shows the coating of a substrate surface with an organosilazane polymer.
  • US Patent 4,751,170 shows the use of ultraviolet rays to react an organic silane compound with an active polymer resist.
  • None of these references, however, shows the process steps of the present invention.
  • According to the present invention a photoresist image is made resistant to reactive ion etching by coating the image with a poly(dimethylsilazane), heating the coated image, and then rinsing with a solvent. The coating may be done by spraying, or by applying in a solvent, such as a hydrocarbon solvent. The process has the advantage of very great simplicity, and requires no vacuum oven or reaction bath. Furthermore, because the reaction is limited to a certain range of resist surfaces, no swelling or cracking appears. This is a great advantage over prior art monomeric silyation agents.
  • Poly(dimethylsilazane) may be used in a hydrocarbon solvent for silylation of resist images. The advantages of polymeric silylating agents are not only a simplified process, but also no swelling of resist images, because they silylate only surfaces of resist images. The silylation with monomeric agents often results in swelling of resist images, making it unsuitable for high resolution lithography.
  • The present invention is particularly useful with phenolic based photoresists. These are very well known in the art. They include, for example, phenol based resins such as novolacs, and poly(hydroxystyrene), made sensitive to radiation by the addition of sensitizers such as esters of 1-oxo-2-diazonaphthalene sulfonic acid.
  • Polysilazanes useful in the present invention are commercially available. They include, for example,
    poly (1,1-dimethylsilazane) (PS112),
    poly (1,2-dimethylsilazane) (MSX114),
    poly (dimethylsilazane) with amino termination (MSX023), and
    the most preferred material, poly( dimethylsilazane) with methoxy termination (MSX022). The expressions PS112, MSX114, MSX023 and MSX022 are the code names for these materials, available from the Petrarch Systems, Bristol, Pa. Except for PS112, all these materials are oliomeric liquids. The methoxy terminated material has the lowest viscosity, and provides the best silylated resist surface with almost zero etch rate for 30 minutes of oxygen reactive ion etching.
  • The heating step of the present process can most conveniently be carried out simply by heating on a hot plate, for about half an hour, at a temperature of about 95°C. Preferred solvents include, for example, toluene and xylene.
  • Resist images were prepared coventionally. A polyimide layer with 2.5 µm thickness was spin-coated on a silicon substrate. On top of this polyimide film, sensitized novolac resist was spin-coated and baked at 85°C for 10 minutes. The images were made by a contact printing with a conventional mask after development in aqueous alkali developer.
  • On top of resist images, the oligomeric liquid poly(dimethylsilazanes) were spray coated and placed on a hot plate at 95°C for 30 minutes. After this heating, the wafers were rinsed with xylene for a short period, several seconds, and dried by a nitrogen stream.
  • The total film thickness of this bilayer consisted of 2.0 µm polyimide and 1.5 µm novolac resist. The film treated by the present reaction showed no thickness loss during 30 minutes of oxygen reactive ion etching, but the untreated film showed severe thickness loss.
  • While the preferred embodiments of the present invention have been illustrated, it should be apparent that modifications and adaptations to those embodiments may occur to one skilled in the art without departing from the scope of the present invention as set forth in the following claims.

Claims (9)

1. A process for making a photoresist image resistant to reactive ion etching, said process comprising the steps of:
i. coating the image with a poly( dimethylsilazane),
ii. heating the coated image, and
iii. rinsing the image with a solvent.
2. A process as claimed in claim 1 wherein the coating is applied by spraying.
3. A process as claimed in claim 1 wherein the coating is applied in a solvent.
4. A process as claimed in claim 1 wherein the photoresist is phenolic resin.
5. A process as claimed in claim 4 wherein the photoresist is a novolac resin.
6. A process as claimed in claim 4 wherein the photoresist is a poly(p-hydroxystyrene).
7. A process as claimed in claim 1 wherein the poly( dimethylsilazane) is an oligomeric liquid.
8. A process as claimed in 5 wherein the poly(dimethylsilazane) is methoxy terminated.
9. A process as claimed in claim 1 wherein the heating is for about half an hour at about 95°C.
EP19900300578 1989-03-17 1990-01-19 Spray silylation of photoresist images Withdrawn EP0387982A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/324,849 US4999280A (en) 1989-03-17 1989-03-17 Spray silylation of photoresist images
US324849 1989-03-17

Publications (2)

Publication Number Publication Date
EP0387982A2 true EP0387982A2 (en) 1990-09-19
EP0387982A3 EP0387982A3 (en) 1991-10-23

Family

ID=23265375

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900300578 Withdrawn EP0387982A3 (en) 1989-03-17 1990-01-19 Spray silylation of photoresist images

Country Status (3)

Country Link
US (1) US4999280A (en)
EP (1) EP0387982A3 (en)
JP (1) JPH02291562A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0476844A1 (en) * 1990-09-21 1992-03-25 Trw Inc. Method for fabricating Josephson tunnel junctions with accurate junction area control
EP0831340A2 (en) * 1996-09-20 1998-03-25 International Business Machines Corporation Stabilised multi-layered structure of colour filters on a silicon chip and a method for making
EP2244127A1 (en) * 2008-01-28 2010-10-27 AZ Electronic Materials (Japan) K.K. Fine pattern mask, method for producing the same, and method for forming fine pattern using the mask

Families Citing this family (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3001607B2 (en) * 1989-04-24 2000-01-24 シーメンス、アクチエンゲゼルシヤフト Dimensionally stable structure transfer method in two-layer method
US5262282A (en) * 1989-06-22 1993-11-16 Kabushiki Kaisha Toshiba Pattern forming method
FI93680C (en) * 1992-05-07 1995-05-10 Outokumpu Instr Oy Support construction for thin film and process for making it
CN1166798A (en) * 1994-11-22 1997-12-03 配合液系统公司 Non-aminic photoresist adhesion promoters for microelectronic applications
EP0833850B1 (en) * 1995-06-22 2000-04-05 Yuri Gudimenko Surface modification of polymers and carbon-based materials
US5667920A (en) * 1996-03-11 1997-09-16 Polaroid Corporation Process for preparing a color filter
US5985524A (en) * 1997-03-28 1999-11-16 International Business Machines Incorporated Process for using bilayer photoresist
JP3426494B2 (en) * 1998-04-02 2003-07-14 沖電気工業株式会社 Method for manufacturing semiconductor device
TW370687B (en) * 1998-04-21 1999-09-21 United Microelectronics Corp Manufacturing method for forming an opening with deep ultra-violet photoresist
US6873087B1 (en) * 1999-10-29 2005-03-29 Board Of Regents, The University Of Texas System High precision orientation alignment and gap control stages for imprint lithography processes
AU2001273491A1 (en) * 2000-07-16 2002-02-05 Board Of Regents, The University Of Texas System High-resolution overlay alignment methods and systems for imprint lithography
US6696220B2 (en) * 2000-10-12 2004-02-24 Board Of Regents, The University Of Texas System Template for room temperature, low pressure micro-and nano-imprint lithography
KR100827741B1 (en) * 2000-07-17 2008-05-07 보드 오브 리전츠, 더 유니버시티 오브 텍사스 시스템 Method and system of automatic fluid dispensing for imprint lithography processes
EP1309897A2 (en) * 2000-08-01 2003-05-14 Board Of Regents, The University Of Texas System Methods for high-precision gap and orientation sensing between a transparent template and substrate for imprint lithography
US20050274219A1 (en) * 2004-06-01 2005-12-15 Molecular Imprints, Inc. Method and system to control movement of a body for nano-scale manufacturing
US20060005657A1 (en) * 2004-06-01 2006-01-12 Molecular Imprints, Inc. Method and system to control movement of a body for nano-scale manufacturing
US6964793B2 (en) * 2002-05-16 2005-11-15 Board Of Regents, The University Of Texas System Method for fabricating nanoscale patterns in light curable compositions using an electric field
US7037639B2 (en) * 2002-05-01 2006-05-02 Molecular Imprints, Inc. Methods of manufacturing a lithography template
US20030235787A1 (en) * 2002-06-24 2003-12-25 Watts Michael P.C. Low viscosity high resolution patterning material
US6926929B2 (en) 2002-07-09 2005-08-09 Molecular Imprints, Inc. System and method for dispensing liquids
US7077992B2 (en) * 2002-07-11 2006-07-18 Molecular Imprints, Inc. Step and repeat imprint lithography processes
US6908861B2 (en) * 2002-07-11 2005-06-21 Molecular Imprints, Inc. Method for imprint lithography using an electric field
US6932934B2 (en) 2002-07-11 2005-08-23 Molecular Imprints, Inc. Formation of discontinuous films during an imprint lithography process
US6900881B2 (en) 2002-07-11 2005-05-31 Molecular Imprints, Inc. Step and repeat imprint lithography systems
US7019819B2 (en) 2002-11-13 2006-03-28 Molecular Imprints, Inc. Chucking system for modulating shapes of substrates
US7070405B2 (en) * 2002-08-01 2006-07-04 Molecular Imprints, Inc. Alignment systems for imprint lithography
US7027156B2 (en) 2002-08-01 2006-04-11 Molecular Imprints, Inc. Scatterometry alignment for imprint lithography
US6916584B2 (en) 2002-08-01 2005-07-12 Molecular Imprints, Inc. Alignment methods for imprint lithography
US7071088B2 (en) * 2002-08-23 2006-07-04 Molecular Imprints, Inc. Method for fabricating bulbous-shaped vias
US8349241B2 (en) * 2002-10-04 2013-01-08 Molecular Imprints, Inc. Method to arrange features on a substrate to replicate features having minimal dimensional variability
US6929762B2 (en) * 2002-11-13 2005-08-16 Molecular Imprints, Inc. Method of reducing pattern distortions during imprint lithography processes
US6980282B2 (en) * 2002-12-11 2005-12-27 Molecular Imprints, Inc. Method for modulating shapes of substrates
US6871558B2 (en) * 2002-12-12 2005-03-29 Molecular Imprints, Inc. Method for determining characteristics of substrate employing fluid geometries
US20040168613A1 (en) * 2003-02-27 2004-09-02 Molecular Imprints, Inc. Composition and method to form a release layer
US7452574B2 (en) * 2003-02-27 2008-11-18 Molecular Imprints, Inc. Method to reduce adhesion between a polymerizable layer and a substrate employing a fluorine-containing layer
US7122079B2 (en) * 2004-02-27 2006-10-17 Molecular Imprints, Inc. Composition for an etching mask comprising a silicon-containing material
US7179396B2 (en) * 2003-03-25 2007-02-20 Molecular Imprints, Inc. Positive tone bi-layer imprint lithography method
US20040197710A1 (en) * 2003-04-01 2004-10-07 Ching-Yu Chang Method for defining ring pattern
US7396475B2 (en) * 2003-04-25 2008-07-08 Molecular Imprints, Inc. Method of forming stepped structures employing imprint lithography
US20050160934A1 (en) * 2004-01-23 2005-07-28 Molecular Imprints, Inc. Materials and methods for imprint lithography
US7157036B2 (en) * 2003-06-17 2007-01-02 Molecular Imprints, Inc Method to reduce adhesion between a conformable region and a pattern of a mold
US7136150B2 (en) * 2003-09-25 2006-11-14 Molecular Imprints, Inc. Imprint lithography template having opaque alignment marks
US7090716B2 (en) * 2003-10-02 2006-08-15 Molecular Imprints, Inc. Single phase fluid imprint lithography method
US8211214B2 (en) * 2003-10-02 2012-07-03 Molecular Imprints, Inc. Single phase fluid imprint lithography method
US20050084804A1 (en) * 2003-10-16 2005-04-21 Molecular Imprints, Inc. Low surface energy templates
US8076386B2 (en) * 2004-02-23 2011-12-13 Molecular Imprints, Inc. Materials for imprint lithography
US7906180B2 (en) 2004-02-27 2011-03-15 Molecular Imprints, Inc. Composition for an etching mask comprising a silicon-containing material
US20050275311A1 (en) * 2004-06-01 2005-12-15 Molecular Imprints, Inc. Compliant device for nano-scale manufacturing
US20050276919A1 (en) * 2004-06-01 2005-12-15 Molecular Imprints, Inc. Method for dispensing a fluid on a substrate
US7281919B2 (en) * 2004-12-07 2007-10-16 Molecular Imprints, Inc. System for controlling a volume of material on a mold
US20060145398A1 (en) * 2004-12-30 2006-07-06 Board Of Regents, The University Of Texas System Release layer comprising diamond-like carbon (DLC) or doped DLC with tunable composition for imprint lithography templates and contact masks
JP4675227B2 (en) * 2005-12-21 2011-04-20 トヨタ自動車株式会社 Method for forming coating film on top surface of convex part
US20090253080A1 (en) * 2008-04-02 2009-10-08 Dammel Ralph R Photoresist Image-Forming Process Using Double Patterning
US20100040838A1 (en) * 2008-08-15 2010-02-18 Abdallah David J Hardmask Process for Forming a Reverse Tone Image
US20100183851A1 (en) * 2009-01-21 2010-07-22 Yi Cao Photoresist Image-forming Process Using Double Patterning
US8084186B2 (en) * 2009-02-10 2011-12-27 Az Electronic Materials Usa Corp. Hardmask process for forming a reverse tone image using polysilazane

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0198215A2 (en) * 1985-03-19 1986-10-22 International Business Machines Corporation A process for rendering a polymeric material resistant to an oxygen-containing plasma
US4678688A (en) * 1983-12-28 1987-07-07 Shin-Etsu Chemical Co., Ltd. Method for forming a surface film of cured organosilicon polymer on a substrate surface
EP0249769A2 (en) * 1986-06-10 1987-12-23 International Business Machines Corporation Patterned image and process for forming a patterned image
EP0260489A2 (en) * 1986-09-18 1988-03-23 International Business Machines Corporation Microlithographic resist containing poly(1,1-dialkylsilazane)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57202533A (en) * 1981-06-09 1982-12-11 Fujitsu Ltd Formation of pattern
JPS5844715A (en) * 1981-09-11 1983-03-15 Fujitsu Ltd Forming method for minute pattern
US4599243A (en) * 1982-12-23 1986-07-08 International Business Machines Corporation Use of plasma polymerized organosilicon films in fabrication of lift-off masks
US4587205A (en) * 1984-04-05 1986-05-06 The United States Of America As Represented By The United States Department Of Energy Method of using polysilane positive photoresist materials
US4552833A (en) * 1984-05-14 1985-11-12 International Business Machines Corporation Radiation sensitive and oxygen plasma developable resist
US4770977A (en) * 1984-09-21 1988-09-13 Commissariat A L'energie Atomique Silicon-containing polymer and its use as a masking resin in a lithography process
US4751170A (en) * 1985-07-26 1988-06-14 Nippon Telegraph And Telephone Corporation Silylation method onto surface of polymer membrane and pattern formation process by the utilization of silylation method
US4770974A (en) * 1986-09-18 1988-09-13 International Business Machines Corporation Microlithographic resist containing poly(1,1-dialkylsilazane)

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4678688A (en) * 1983-12-28 1987-07-07 Shin-Etsu Chemical Co., Ltd. Method for forming a surface film of cured organosilicon polymer on a substrate surface
EP0198215A2 (en) * 1985-03-19 1986-10-22 International Business Machines Corporation A process for rendering a polymeric material resistant to an oxygen-containing plasma
EP0249769A2 (en) * 1986-06-10 1987-12-23 International Business Machines Corporation Patterned image and process for forming a patterned image
EP0260489A2 (en) * 1986-09-18 1988-03-23 International Business Machines Corporation Microlithographic resist containing poly(1,1-dialkylsilazane)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0476844A1 (en) * 1990-09-21 1992-03-25 Trw Inc. Method for fabricating Josephson tunnel junctions with accurate junction area control
EP0831340A2 (en) * 1996-09-20 1998-03-25 International Business Machines Corporation Stabilised multi-layered structure of colour filters on a silicon chip and a method for making
EP0831340A3 (en) * 1996-09-20 1999-07-28 International Business Machines Corporation Stabilised multi-layered structure of colour filters on a silicon chip and a method for making
EP2244127A1 (en) * 2008-01-28 2010-10-27 AZ Electronic Materials (Japan) K.K. Fine pattern mask, method for producing the same, and method for forming fine pattern using the mask
EP2244127A4 (en) * 2008-01-28 2013-10-02 Az Electronic Materials Japan Fine pattern mask, method for producing the same, and method for forming fine pattern using the mask

Also Published As

Publication number Publication date
US4999280A (en) 1991-03-12
EP0387982A3 (en) 1991-10-23
JPH02291562A (en) 1990-12-03

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